Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species

Jesus E. Perea-Buceta; Israel Fernández; Sami Heikkinen; Kirill Axenov; Alistair W.T. King; Teemu Niemi; Martin Nieger; Markku Leskelä; Timo Repo

doi:10.1002/anie.201506216

Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species

Jesus E. Perea-Buceta, Israel Fernández, Sami Heikkinen, Kirill Axenov, Alistair W.T. King, Teemu Niemi, Martin Nieger, Markku Leskelä, Timo Repo

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Research output: Contribution to journal › Article › Scientific › peer-review

16 Citations (Scopus)

Abstract

The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.

Original language	English
Pages (from-to)	14321-14325
Number of pages	5
Journal	Angewandte Chemie: International Edition
Volume	54
Issue number	48
DOIs	https://doi.org/10.1002/anie.201506216
Publication status	Published - 23 Nov 2015
MoE publication type	A1 Journal article-refereed

Keywords

density functional calculations
homogeneous hydrogenation
reaction mechanisms
rhodium(I)
Wilkinson's catalyst

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10.1002/anie.201506216

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abstract = "The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.",

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AU - Fernández, Israel

AU - Heikkinen, Sami

AU - Axenov, Kirill

AU - King, Alistair W.T.

AU - Niemi, Teemu

AU - Nieger, Martin

AU - Leskelä, Markku

AU - Repo, Timo

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AB - The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.

KW - density functional calculations

KW - homogeneous hydrogenation

KW - reaction mechanisms

KW - rhodium(I)

KW - Wilkinson's catalyst

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Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species

Abstract

Keywords

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